Sulphur dyestuffs and process of preparing the same



moleculesinvolved. H i '-By' this invention there is provided'a convenient,

Patented Feb. 20, 1945 mY UNlTE STATES. PATENT FF C 'SULPHU'R DYESTUFFS AND PROCESS, or

. I PREPARING THE SAME Arthur Lawrence Fox, Woodst'own, N. J., assignor to E. I du Pont de Nemours' & Company,

Wilmington, Del., a corporation of Delaware 1 3 No Drawing.

pplication November 21, 194 S'erialNo. 466,483

-i Q Cla ims. (01. 260-133) a complex addition product of these two reagents carefully prepared'rinadv'ance by heating the two reagents together 'insuit'able'ipropor tions by weight. L on? of'the commonestaddition ing in their structure primary, secondary or tertiary amines or nitrogen atoms forming"part of a heterocyclic ring.

It is an object of this invention to provide a new and economical method for the production of sulphur colors. It is a further objectof this invention to provide sulphur colors'not' now known. It is a further object of this invention to convert carbocyclic amines intoinsoluble dye pigments which may be applied to cotton fiber .from a sodium sulfidevat. Other and further important object of this invention 'will appear as the description proceeds.

'-" In the past, sulphur colors have been prepared in general byreactin'g dye intermediates periods-creme,egg 10 to 150 hours.' Other methods employed have included high temperaquickand economical method 'forpreparing sulph'urcolors -by treating aromatic amniocompounds with a complex of sulphur chloride and aluminum chloride which is easily andcheaply ipreparedfland which is extremely reactive. By :this invention itis simply necessary to treat the organic molecule withthis reagent for relatively short periods of time, depending on the activity "of the molecule, and drown the reaction mass.

It has been found in many cases that a reaction period of 5 minutes'fis ample, although .llon'ger' reaction periods'oftenproduce deeper shadesfiof the .dyeand introduce greater amounts of sul- -phur into .themolecule.

.It is worthy'ofnote that treatment of organic compounds with sulphur monochloride .in the presence of aluminum chloride as .a catalyst 'lhasibeen done on various'occasionsin .the'art. "However;thesetreatments did not result in :the .same, productsor mixtures .of product .asfare :cbtainable according to this invention. The .p'roductsfromsaid older procedures were not'dye- ,-stufis,yand their chlorine. content was generally method havebeen"destructive tothe organic;

with sodium 'polysulfid'e over extremely long r much larger than inthe reactionproductsof this invention. I r

.Th'e distinctiveieatureof my present invention is that instead of using amixture of sulphur monochloride and aluminum chloride, I employ ing agent.

m b purpose of analysis, the crude materialspurified by extraction with caustic may be further'exproducts thus obtained is a complex of constituchlorine, but is otherwisebf the same general nature as in the invention.

' The characteristic of the novel compounds obtained according to this invention is that they are colored bodies of the sulphur dyestufi class. In order words, they may be reduced with aqueous sodium sulphide to produce a,.sulphur dye vat," which has afiinityfor textile fiber, and which may be oxidized on'the fiber into dyeings of good fastness qualities. I

The crude reaction products of this invention are isolated by drowning th reaction mass in water or on ice and may be purified by extraction with dilute alkali. .This dissolves the aluminum as sodium aluminateand converts any precipipreferred embodiments" of ithis .tate of sulphur to sodium sulphide ;or' sodium sulphhydrate. It has been found that many of the sulphur colors made-by this procedure are so easily vattabl withsodium sulphide that the sodium sulphide produced in the action of the serum hydroxide on thesulphurin' the ,iirowned ude "product ca ses co or It at? nsequently, in somecases, it is'nec'essary' toisolate the sulphur color by an oxidative procedure, such asblowing How v r, man of the oth g e f r a e hotv t d by he low ii c tratip f d phideii rme iil h extrac i 'a isolatedfdirectly by filtration. Forflthe tracted with carbon disulfide to remove any free sulfur. I

,As already indicated, the dyes made according ,to'this invention may be converted into soluble leuco derivatives by heating with sodium sulphide solutions. It has beenfoundadvisable in many cases to vat the dye byheatingthe dry'material ,with ,sodiumsulphidemelted inits own water of crystallization. This concentrated solution easily vatsthe dye1and on dilution completely soluble leuco vats are-obtained. ,Thesemay be employed todye cotton and rayon. In other case'swool, silk, and nylonhavebeen dyed,,but duetothealkalinity .ofthe vat, great care mustlbe exercised notto destroy the fiber.

The following examples are given to withair or treatment Withan oxidizillustrate this invention, without any intent however to limit my invention to the details of procedure. Parts mentioned are by weight.

Part A.-Preparation of the aluminum-chloride-sulphur-chloride complex.

1975 parts of aluminum chlorid (AlCls) and 4215 parts of sulphur monochloride (S2012) were mixed and heated at 90-95 C. for 36 hours. The reaction mass on cooling was a dark brown liquid comprising the sulphur chloride-aluminum chloride complex.

.Part B.Preparation of novel sulphur colors.

Example 1 100 parts of meta-toluylene diamine were reacted at room temperature with 600 parts of the aluminum-chloride-sulphur-monochloride complex prepared in Part A. The temperature rose spontaneously to about 100 C. and there resulted a sulphur color dyeing cotton from a, sodium sulphide vat a light tan shade.

Example 2 100 parts of para-hydroxyrphenyl-beta-naphthylamine were reacted with 600 parts of the above mentioned aluminum-chloride-sulphur monochloride complex for one hour at 100 C. A greenish black dye was obtained possessing fair wash fastness.

Example 3 100 parts of 2,4-dinitro-4-hydroxy-diphenylamine were reacted with 600 parts of the aluminum-chloride-sulphur-monochloride complex at 100 C. for one hour. There was obtained a rich chocolat brown sulphur color which dyed cotton from a, sodium sulphide bath.

Example 4 100 parts of ara-ethoxy-p'-hydroxy-diphenylamine were reacted with 600 parts of the above aluminum-chlcride-sulphur-monochloride complex for one hour at 100 C. It gave a gray blue dyestuff dyeing cotton from a sodium sulphide bath.

Example 5 100 parts of para-toluidine were reacted with 600 parts of the aluminum-chloride-sulphurmonochloride complex for one hour at 100 C. and gave on working up a yellow sulphur color.

Example 6 20 parts of formaldehyde aniline were reacted with 120 parts of the aluminum-chloride-sulphurmonochloride complex at 110 C. for four hours. This introduced 3 atoms of sulphur into the molecule, and the-product dyed cotton a tan shade.

Example 7 chloride class or of the aluminum chloride class, optimum temperature, duration of the reaction, substituents in the initial organic material to be sulphurized, and other details. All these variations may-be practiced with the invention set forth in the instant application.

I claim as my invention:

1. The process of preparing a sulphur type dyestuff, which comprises reacting a carbocyclic compound having at least one basic. nitrogen atom with the complex compound obtainable by reacting aluminum chloride With sulphur monochloride at elevated temperature and in the absenc of a solvent.

2. The process of preparing a sulphur type dyestuff, which comprises reacting an aromatic compound having at least one basic nitrogen atom with the complex compound obtainable by heating aluminum chloride with substantially two moles of sulphur monochloride at elevated temperature and in the absence of a solvent.

3. The process of preparing a sulphur type dyestuff, which comprises reacting an aromatic primary amin with th complex compound obtainable by heating aluminum chloride with substantially two moles of sulphur monochloride at elevated temperature and in the absence of a solvent.

4. The process of preparing a sulphur type dyestuff, which comprises reacting a diaryl amine With the complex compound obtainable by heating aluminum chloride with substantially two moles of sulphur monochloride at elevated temperature and in the absence of a solvent.

5. The sulphur-containing compounds obtainable by reacting with the complex addition product of aluminum chloride and sulphur monochlorid having the formula AlCl3.2S2C12 upon aromatic nitrogenous bases, said compounds being colored bodies, soluble in aqueous sodium sulphide solution and being capable of dyeing cotton from said solution by the standard sulphur-vat dye process.

6. As a new dyestuif, the reaction product of an aluminum-chloride sulphur monochloride complex of constitution AlCl3.2S2C12 upon an arcmatic primary amine, said dyestufi being soluble in the sodium sulphid vat and being capable of dyeing cotton therefrom by the sulphur-vat dye process. 7

7. As a new dyestufi, the reaction product of an aluminum-chloride sulphur monochlorid complex of constitution A1C13.2S2C12 upon a diaryl amine, said dyestufi being soluble in the sodium sulphide vat and being capable of dyeing cotton therefrom by the sulphur-vat dye process.

8. As a new compound, the reaction product of an aromatic compound having at least one basic nitrogen atom with the aluminum-chloride-sulphur-monochloride complex represented by the formula A1Cl3.2S2C12, said compound being a colored body capable of dyeing textile material by the sulphur-vat process.

9. The dyestuff obtained by reacting 1 part of carbazole with 6 parts of an aluminum-chloridesulphur-monochloride complex of constitution A1Cl3.2S2C12, at the boiling point of the reaction mass, said dyestufl? being characterized by its capacity to dye cotton from a sodium sulphide vat to a rich golden brown color.

"ARTH-UR LAWRENCE FQX. 

